Organic hydroperoxides can be prepared by oxidizing arylalkyl hydrocarbons having a tertiary hydrogen with an oxygen containing gas. For example, the well known cumene hydroperoxide process employs air oxidation of cumene at a temperature of 80°-130° C. and elevated pressure with promoters such as sodium hydroxide or carbonate, followed by cleavage of the cumene hydroperoxide at 60°-100° C. with agitation under acidic conditions that can include a non-oxidizing acid such as sulfur dioxide gas. The resulting mixture of phenol, acetone and various byproducts is neutralized and separated to recover phenol and acetone in approximately equimolar proportions.
There are drawbacks to the cumene hydroperoxide process. Notably, the economics of the process for phenol production are tied to the market for acetone. The use of another arylalkyl hydrocarbon with an alkyl group other than isopropyl would yield a different ketone, however, air oxidation of such other arylalkyls can be problematic. The use of catalysts or other promoters to improve oxidation conversion rates and yields can complicate the downstream purification and/or cleavage reactions. The economics could be improved by the use of an oxidation promoter system that could be easily prepared, recovered and recycled.